Azo dyestuffs and method of making same



Patented Sept. 13, 1932 UNITED STATES COMPANY, OF MIDLAND, MICHIGAN, A CORPORATION OF PATENT orrice MICHIGAN AZO DYESTUFFS AND METHOD OF MAKING SAME No Drawing.

The present invention relates to certain new compounds derived from phenyl-anaphthyl ether, viznitro-, aminoand azo derivates thereof, the last named being useful dyestuffs for which the first two are intermediate products, together with methods for the preparation of such compounds.

In my pending application Serial No. 289,- 081, filed June 28, 1928, I have described and claimed certain sulphonic and. nitro-sul: phonic acid derivatives of the abovementioned phenyl-a-naphthyl ether, and also, incidens tally, have referred to a mono-nitro derivative of said ether. It is amongthe objects of the present application to describe more particularly the steps for the preparation of said mono-nitro derivative. Another object is to describe the preparation of the corresponding aminoderivative and of azo derivatives to be prepared therefrom by diazotizing such amine and couplin with suitable arylresidues. A further ject is to describe more particularly the preparation of such azo derivatives which are formed by coupling with arylides of 2.3-hydroXy-naphthoic acid. Generally speaking, the azo derivatives which are included in the subject matter of,

the present application are useful dyestuffs, and especially those derivatives containing as one component an arylide of the aforesaid 2,3-hydroXy-naphthoic acid. To the accomplishment of the foregoing and related ends, the invention, then, consists of the new products, together with the steps involved .in making such products, hereinafter fully described and particularly pointed out in the claims, the following description setting forth but several of the various ways in which the principle of theinvention may be used. 1

Preliminary to the preparation of the azo dyestuffs herein described I make the requisite intermediate compounds by first nitrating phenyl-a-naphthyl ether and then reducing the mono-nitro compound so obtained to form the mono-amino compound. The nitration of the aforesaid ether according to the usual procedure does not yield satisfac: tory results, owing largely to the relative insolubility of the ether and its nitro derivative Application filed March 19, 1929. Serial No. 348,362.

in an aqueous medium. I have found that far better results are realized when the nitra-v tion is carried out in a medium of glacial 1acetic acid. Accordingly I proceed as folows; Y 1

I dissolve 1 mole phenyl-a-naphthyl, ether in 6 parts by weight glacial acetic acid and then add gradually with stirring 1 mole concentrated nitric acid diluted with 2 parts by weight glacial acetic acid, maintaining the temperature below C. After all of the nitric acid has beenadded, stirring is contin ued for about 1/2 hour longer, then ice water to the amountof about 1/10'to 1/5 of the volume of the reaction'mixture is added. The mono-nitro compound separates as a precipitate of yellow crystal flakes, which. are filtered from the mother liquor and washed with water. If the liquor is made more dilute, thecrystal product is obtained in a less pure form. .The product recrystallized from alcohol or acetic acid has M. P. 9394 (l.

Probableformula;- 1

The reduction of the nitro compound for the preparation performed in the usual way, viz

A mixture I consisting of 200: parts by Weight iron filings, 400 parts'water and 6 parts by weight concentrated hydrochloric acid is heated with stirring while .100 parts by weight of the nitro compound are gradually added. When the mixture has become colorless, it is neutralized with sodiumcarbonate, filtered and the amino compound is extracted with benzene or other suitable solvent. The benzeneextractis dried, thebenzene distilled off and finally the amine distilled invacuum. It forms salt is only very slightly soluble in, water-.

From the amino compound-the diazo derivative is prepared and the -.latter;may then ple W t a uitabl ar a i i e or phenol. I have found that when coupled with arylides. of 2.3-hydroxy-napht-hoic, 1 acid of the amino compound is colorless crystals, M. P. 54 C. The hydrochloric acid ERNEST F. GRETHER, 0F MIDLAND, MICHIGAN, Assrenoa TO THE Dow CHEMICAL in dilute hydrochloric acid, adding a solution containing 7 parts by Weight sodium nitrite and then adding alkali carbonate or acetate until the solution is almost neutralized. The

previously treated material is then immersed in the diazo solution in the cold. The dye is developed directly on the'fibre, a clear deep shade of violet red, possessing very good fastness to light and'washing. The compound has probably the following struotural formula;

While a fast dyeing is readily achieved without the aid of mordants, the use of various substances for the purpose of fixing the dye, or promoting its absorption by the fibre,

' or modifying the color tone thereof, in connection with the procedure above described is equally comprehended'within the invention. For example, after-treatment with chromium or copper salts introduces a definite color modification in softer and less brilliant tones. v v

In similar fashion I have prepared other dyes of this same type, as shown in the appended table, wherein the first column lists the particular arylides of 2.3-hydroxy-naphthoic acid that were coupled with the diazo derivative of '1 -amino--phenoxy-naphthalene and the second column shows the color shade produced on the dyed material.

l-aminoA-phenoxy-naphthalene diazotized and coupled with arylide of 2.3-hydroxy acid W 0010:

from:-

a.-naphthylamine Deep violet red Diamino-diphenyl ether Deep red Ortho-nitro-para-phenetidine Brownsih red 3,4 diehloraniline Purple violet V Meta-nitraniline Purple violet Para-phenetidine i. Violet red Ortho-chlor-para-nitraniline s Reddlsh brown The typical formula for the dyes. of the hydroxy-naphthoic acid anilide.

present description may be expressed as follows, wherein R represents an aryl residue which may be further substituted, as for ex ample, by halogen, nitro, amino, hydroxy or alkoxy groups;

likewise included within the invention' to introduce furtherv substituent groups intojthephenyl and/or naphthyl nuclei of the 1-amino-4-phenoxy-nzipthalene component of the present group of newdyestuffs.

Although in the specific example given above I have described the treatment of the cotton fibre,I may apply these dyes to other textile fibres of Vegetable oranimal origin, such as'silk, or' to synthetically prepared fibres, suchas rayon'or the like.

It .fisrfurther withinithe purview of my invention to prepare dyes of the presenttype in substance, as well as to develop same in situ on the fibre. That is to say, the soluti ons' of therespeotive reaction components may berbrought'together directly, the dye then being precipitated from the aqueous reaction mixture and separated therefrom by anyconvenient means. Owingto their insolubility, stabilityand fastness to lightand Water, these 'dye'compounds may also be used as plgments. V V Other modes of applyingthe'principle of my invention may beemployed instead of the oneexplained, change being made as regards the materials employed, provided the ingredients stated by any of the following claimsor the equivalent of such stated ingredients be employed. 7 Y

I therefore partcularly .pointout and distinctly claim asmy invention':- i

1. The'method of making new azo dyestuffs which comprises diazotizing ,l-amino-Lphenoxy-naphthalene and coupling with an arylide of 2.3-hydroxy-naphthoie acid.

2. The method of making new azo dyestufis Which comprises diazotizing l-amino-et-phenoxy-naphthalene and coupling. with 2.3-

As anew prod ct, an azo dyestufi ha P ly the-formula;-

4. As a new product, an azo dyestuff having probably the formula;

5. The method of making new azo dyestuffs which comprises diazotizing amino-alphaphenoxy-naphtha1ene having the general formula O HzN and coupling with an arylide of 2.3-hydroxynaphthoic acid.

6. As a new product, an azo dyestufi having the general formula 

